CN106732733A - A kind of application of preparation and its catalysis o-chloronitrobenzene hydrogenation reaction of nitrogen-doped carbon coated core-shell structure dilval nanocatalyst - Google Patents
A kind of application of preparation and its catalysis o-chloronitrobenzene hydrogenation reaction of nitrogen-doped carbon coated core-shell structure dilval nanocatalyst Download PDFInfo
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- CN106732733A CN106732733A CN201710017515.6A CN201710017515A CN106732733A CN 106732733 A CN106732733 A CN 106732733A CN 201710017515 A CN201710017515 A CN 201710017515A CN 106732733 A CN106732733 A CN 106732733A
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- dilval
- nanocatalyst
- nitrogen
- shell structure
- doped carbon
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000011258 core-shell material Substances 0.000 title claims abstract description 32
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000011790 ferrous sulphate Substances 0.000 claims description 8
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 8
- 239000000084 colloidal system Substances 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- YFGRSOGKVQIGKG-UHFFFAOYSA-N [Cl].NC1=CC=CC=C1 Chemical group [Cl].NC1=CC=CC=C1 YFGRSOGKVQIGKG-UHFFFAOYSA-N 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 46
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003575 carbonaceous material Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 9
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 229910000863 Ferronickel Inorganic materials 0.000 abstract description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 4
- 238000002955 isolation Methods 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract 1
- 125000001475 halogen functional group Chemical group 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 150000007974 melamines Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- -1 Aromatic halogenated benzene amine Chemical class 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical class ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/615—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
Abstract
Preparation method and its application of catalysis o-chloronitrobenzene hydrogenation reaction the invention provides a kind of nitrogen-doped carbon coated core-shell structure dilval nanocatalyst of catalyst technical field.Methods described is synthesized with the ferronickel layered double hydroxide precursor that particle diameter is small, surface energy is high by nucleation crystallization isolation method first, gone uniformly to mix with melamine and dicyandiamide mixing carbon material precursor again, new nitrogen-doped carbon coated core-shell structure dilval nanocatalyst is prepared finally by high temperature autoreduction.By its efficient application in nitrohalogen compound catalytic hydrogenation generation halo aniline reaction in, the conversion ratio of o-chloronitrobenzene and to o-chloraniline selectivity selectivity respectively up to 95~100% and 98~100%.The new nitrogen-doped carbon coated core-shell structure dilval nanocatalyst structure novel and unique, technique green energy conservation, and catalyst structure stabilization, are with a wide range of applications.
Description
Technical field
The invention belongs to catalyst technical field, more particularly to a kind of nitrogen-doped carbon coated core-shell structure dilval nanometer
The preparation of catalyst and the method for o-chloronitrobenzene hydrogenation reaction.
Background technology
Aromatic halogenated benzene amine has important application at aspects such as medical synthesis, dyestuff, medicine, but by halonitro
During compound catalytic hydrogenation generation halo aniline, the fracture of C-Cl keys is easier to be occurred, and causes the yield of halo aniline
Substantially reduce.Therefore, nitrohalogen compound selective hydrogenation generation halo aniline is particularly important.People are more, and application noble metal is urged
Agent such as Pd, Au, Pt etc. carry out this reaction (J.Lyu, J.Wang, C.Lu, L.Ma, Q.Zhang, X.He, and X.Li.Size-
dependent halogenated nitrobenzene hydrogenation selectivity of
Pdnanoparticles[J].J.Phys.Chem.C.,2014,118(5):2594-2601.,D.He,H.Shi,Y.Wu and
B.Q.Xu.Synthesis of chloroanilines:selective hydrogenation of the nitro in
chloronitrobenzenes over zirconia-supported gold catalyst[J].Green.Chem.,
2007,9(8):849-851.,B.Zhao,C.J.Chou and Y.W.Chen.Hydrogenation of p-
chloronitrobenzene on tungsten-modified NiCoBcatalyst[J].Ind.Eng.Chem.Res.,
2010,49(4):1669-1676.), but because noble metal is expensive, earth reserves are rare and are difficult to the shortcoming for reclaiming,
Exploitation base metal is a necessary job.At present, nickel based metal catalyst due to high activity and selectivity and into
This low advantage is widely used in catalytic hydrogenation field, wherein, carbon fiber loaded Ni bases catalyst, nickel base amorphous alloy catalysis
Agent all shows preferable catalysis activity.
Laminated type bimetal hydroxide compound (LDHs) is the two-dimensional layer clay material of a class high-sequential, its laminate by
Cation composition, the species and ratio of cation have adjustable denaturation, and interlayer is then made up of anion and is kept so as to reach electric charge
Perseverance (Carrado K A, Kostapapas A, Suib S L.Layered double hydroxides (LDHs) [J]
.Solid.State.Ionics.,1988,26(2):77-86.,Fan G,Li F,Evans D G,Duan X.Catalytic
applications of layered double hydroxides:recent advances and perspectives
[J].Chem.Soc.Rev.,2014,43(20):7040-7066.).This advantage of LDHs materials makes it have in catalytic field
It is widely used, is good catalyst precarsor.For example, because the cation arrangement on its laminate is uniform and in order, leads to
Cross after calcining restores, the load type metal catalyst for obtaining has polymolecularity.Such metallic catalyst has higher
Heat endurance, big specific surface, abundant pore structure and can modulation surface acidic-basic property, the catalysis of catalyst can be significantly improved
Performance.
N atoms are mixed and can be formed after carbon material the carbon material of N doping, and being entrained in hexagonal carbon grid for N atoms is produced
Localised tension, causes carbon structure to deform, and is born because the lone pair electrons of N atoms can supply sp2 hydridization carbon skeletons delocalized pi-bond
Electric charge, so as to strengthen electron transport property and chemical reactivity；The N atoms of doping electron rich can change material in carbon material
The band structure of material, making the valence band of carbon material reduces, the chemical stability of reinforcing material, and the electronics increased on fermi level is close
Degree.Nitrogen enters into the nitrogen-doped porous carbon material that the internal structure of carbon material is formed, except all excellent with carbon material
Point is outer, with the machinery of its uniqueness, electronics, optics, semiconductor, energy storage property, it is suitable alkaline the features such as, in superhard material, suction
The range of application of the aspect such as attached, catalysis and fuel cell further expands.
The present invention establishes a kind of preparation side of the core shell structure dilval nanocatalyst of new nitrogen-doped carbon cladding
Method.With ferronickel LDHs with nitrogen-doped carbon mixing precursor (melamine and dicyandiamide) compound as catalyst precarsor, by inertia
Atmosphere high temperature autoreduction generates the core shell structure dilval catalyst of new nitrogen-doped carbon cladding, and nitrogen-doped carbon shell not only may be used
Strengthen electron transport property and chemical reactivity with by the strong interaction between dilval, ferronickel can also be suppressed
The growth and reunion of alloy nano particle.Catalyst table in nitrohalogen compound selectively produces the reaction of halo aniline
Reveal catalysis activity higher, the structure novel and unique of the preparation method and catalyst has great application prospect and studies
Value.
The content of the invention
The present invention is intended to provide a kind of method that autoreduction method prepares core shell structure non-noble metal alloy nanocatalyst, solution
Noble metal catalyst of having determined is expensive, easy inactivation of reuniting, stability is poor, the problems such as need additional reducing agent, use it for
Nitrohalogen compound catalytic hydrogenation generates halo aniline.
The preparation scheme of catalyst is as follows in the present invention：Being synthesized by nucleation crystallization isolation method first has that particle diameter is small, table
Face energy NiFe-LDH precursors high, then gone uniformly to mix with melamine and dicyandiamide mixing carbon material precursor, finally lead to
Cross high temperature autoreduction and prepare new nitrogen-doped carbon coated core-shell structure dilval nanocatalyst, wherein, dilval
The average grain diameter of nano particle is 5~20nm, and specific surface is 80~150m2/g；The weight/mass percentage composition of Ni is in catalyst
The weight/mass percentage composition of 20%~40%, Fe is 8%~14%.
A kind of preparation method of nitrogen-doped carbon coated core-shell structure dilval nanocatalyst：
1) by nickel nitrate and ferrous sulfate mixed aqueous solution, NaOH and H2O2Mixed aqueous solution is placed in colloid mill in equal volume
After being sufficiently stirred for 1-5min, it is transferred in polytetrafluoroethylliner liner, closed rear room temperature static crystallization 12-36h, after reaction terminates,
To neutrality, freeze-drying obtains NiFe-LDH precursors to centrifuge washing；
2) prepared NiFe-LDH precursors are mixed with melamine and dicyandiamide mixture, is placed in nitrogen atmosphere
In stove, 2-10h is incubated at being warming up to 500~650 DEG C, obtains nitrogen-doped carbon coated core-shell structure dilval nanocatalyst.
Preferably, step 1) in, the Ni of nickel nitrate and ferrous sulfate mixed aqueous solution2+Concentration be 0.03~0.1mol/
L。
Preferably, step 1) in, the Fe of nickel nitrate and ferrous sulfate mixed aqueous solution2+Concentration be 0.01~0.04mol/
L。
Preferably, step 1) in, NaOH and H2O2The concentration of NaOH is 0.06~0.23mol/L in mixed aqueous solution.
Preferably, step 1) in, NaOH and H2O2In mixed aqueous solution, H2O2Consumption be dense with ferrous sulfate mole
The ratio between degree is 1~2.5：1.
Preferably, step 2) in, nanocatalyst precursor is 0.5 with the mass ratio of melamine and dicyandiamide mixture：2
~1, the mol ratio of melamine and dicyandiamide is 0.3：0.7~1.
The nitrogen-doped carbon coated core-shell structure dilval nanocatalyst of above-mentioned preparation is used to be catalyzed o-chloronitrobenzene
Hydrogenation reaction.The reaction condition is：The second of nitrogen-doped carbon coated core-shell structure dilval nanocatalyst and o-chloronitrobenzene
Alcoholic solution is added in autoclave, leads to the H of 0.5MPa2, temperature rises to 80 DEG C of reactions.
Preferably, reaction 3h after, the conversion ratio of o-chloronitrobenzene and to o-chloraniline selectively be respectively 95~100% Hes
98~100%.
Nitrogen-doped carbon coated core-shell structure dilval nanocatalyst to obtaining carries out structural characterization.By transmission electron microscope
(TEM) figure can be found that catalyst has typical core shell structure, and its core is made up of metal nanoparticle, and particle diameter is consistent, distribution
Uniformly, its shell is made up of carbon material；By XRD spectra as can be seen that occurring in that the diffraction maximum of typical dilval；By scanning
Transmission electron microscope (STEM) figure can be found that catalyst particle size is consistent, is evenly distributed, Ni and Fe location overlaps, it was demonstrated that Ni and Fe are formed
Nano metal alloy particle.
The present invention successfully prepares the short grained LDH of different ferronickel ratios, uniform particle sizes, system by nucleation crystallization isolation method
Preparation Method is fast and simple；LDH is well mixed with nitrogenous cyanamide precursor, autoreduction successfully synthesizes core shell structure in atmosphere furnace
Dilval catalyst, the size of catalyst particle size can be regulated and controled by changing ferronickel ratio；N atoms in the carbon shell of N doping
Lone pair electrons can supply sp2 hydridization carbon skeleton delocalized pi-bond negative electrical charges, simultaneously because strong between dilval and shell
Interact, cause the electronics in dilval to be shifted to carbon skeleton, the synergy of both enhances the electronics of catalyst
Transmission characteristic and chemical reactivity；The dilval active component of catalyst with core-casing structure is wrapped up and protected by carbon nitrogen shell,
Strong interaction between the two makes it have stability higher；Based between dilval core and the carbon shell of N doping
Strong interaction, and small particle catalyst strong solution from hydrogen ability so that catalyst shows that catalysis higher is lived
Property.
Brief description of the drawings
Fig. 1 is the XRD spectra of core shell structure dilval catalyst prepared by embodiment 1.
Fig. 2 is TEM the and STEM spectrograms of core shell structure dilval catalyst prepared by embodiment 1.
Fig. 3 is the N of core shell structure dilval catalyst prepared by embodiment 12Adsorption/desorption curve figure.
Fig. 4 is for o-chloronitrobenzene conversion ratio in embodiment 1 and to o-chloraniline selectivity time history plot.
Specific embodiment
Embodiment 1
By 4.04gFe (NO3)3·9H2O、8.724gNi(NO3)2·6H2O is dissolved in 100mL deionized waters, ultrasonic 5min,
It is sufficiently mixed, is designated as solution first.
By the 2.56g NaOH and H of 125 μ L mass fractions 30%2O2It is dissolved in 100mL deionized waters, ultrasonic 5min, fully
Mixing, is designated as solution second.
Two kinds of solution are slowly mixed together and are added in colloid mill at room temperature, rotating speed is controlled for 3000rpm, with 2min
It is transferred in polytetrafluoroethylliner liner after being stirred vigorously, closed rear room temperature static crystallization 24h, after reaction terminates, centrifuge washing is extremely
Neutrality, freeze-drying obtains the NiFe-LDH precursors of nanocatalyst.
0.5gNiFe-LDH is taken to be fully ground to it in mortar and mixed with 0.19g dicyandiamides and 1.31g melamines
It is even, it is placed in porcelain boat, 5 DEG C of min in nitrogen atmosphere-1It is warming up to 500 DEG C and is incubated 6h, core shell structure is obtained after grinding
Nanocatalyst, the wherein average grain diameter of dilval nano particle are 13nm, the weight/mass percentage composition of nickel element in catalyst
It is that the weight/mass percentage composition of 27.5%, Fe is 9.1%, the specific surface area of catalyst is 142m2/g。
In o-chloronitrobenzene selective hydrogenation, first to addition 0.1g catalyst, 50ml ethanol, 0.5g in reactor
O-chloronitrobenzene.Then, tighten reactor, ventilation 10 times filled with hydrogen, it is ensured that be full of hydrogen in system, and build the pressure one hour with
Ensure the seal of reactor.Hydrogen to system pressure 0.5MPa is finally passed through, unlatching is stirred and rises to 80 DEG C and starts reaction.Plus
When hydrogen reaction proceeds to 3h, the conversion ratio of o-chloronitrobenzene has reached 100%, and the selectivity of o-chloraniline is 99.6%.
Catalyst with core-casing structure to obtaining carries out structural characterization test.Fig. 1 is catalyst X-ray diffraction (XRD) spectrogram.
By figure it can clearly be seen that dilval is in corresponding 111,200,220 crystal face of 44.28 ° of 51.53 ° of 75.87 ° of difference.Melamine
Amine can discharge reducibility gas NH in 500 DEG C of calcination process3, the gas can restore the Ni in LDH structures and Fe
Come, while Ni and Fe form NiFe alloy form.Fig. 2 is the transmission electron microscope (TEM) of catalyst described in embodiment 1
With scanning transmission electron microscope (STEM) picture, it can be seen that dilval particle size average out to 12.5nm, and success shape
Into dilval nano-particle.Fig. 3 is the N of catalyst2Adsorption desorption curve map, as can be seen from the figure it belongs to IV types, and goes out
Existing H1 type hysteresis loops, illustrate that material belongs to typical meso-hole structure.Fig. 4 is the adjacent chlorine nitre that the catalyst that embodiment 1 is obtained is measured
The curve that the selectivity of base benzene conversion ratio and o-chloraniline is changed over time.
Embodiment 2
By 4.04gFe (NO3)3·9H2O、5.816gNi(NO3)2·6H2O is dissolved in 100mL deionized waters, ultrasonic 5min,
It is sufficiently mixed, is designated as solution first.
By the 2.56g NaOH and H of 125 μ L mass fractions 30%2O2It is dissolved in 100mL deionized waters, ultrasonic 5min, fully
Mixing.It is designated as solution second.
Two kinds of solution are slowly mixed together and are added in colloid mill at room temperature, rotating speed is controlled for 3000rpm, with 2min
It is transferred in polytetrafluoroethylliner liner after being stirred vigorously, closed rear room temperature static crystallization 24h.After reaction terminates, centrifuge washing is extremely
Neutrality, freeze-drying obtains the-LDH precursors of nanocatalyst.
0.5gNiFe-LDH is taken to be fully ground to it in mortar and mixed with 0.19g dicyandiamides and 1.31g melamines
It is even, it is placed in porcelain boat, 5 DEG C of min in nitrogen atmosphere-1It is warming up to 500 DEG C and is incubated 6h, core shell structure is obtained after grinding
Catalyst.Wherein dilval nano-particle average grain diameter is 8nm, and the weight/mass percentage composition of nickel element is in catalyst
The weight/mass percentage composition of 22.5%, Fe is 10.6%, and the specific surface area of catalyst is 127m2/g。
In o-chloronitrobenzene selective hydrogenation, first to addition 0.1g catalyst, 50ml ethanol, 0.5g in reactor
O-chloronitrobenzene.Then, tighten reactor, ventilation 10 times filled with hydrogen, it is ensured that be full of hydrogen in system, and build the pressure one hour with
Ensure the seal of reactor.Hydrogen to system pressure 0.5MPa is finally passed through, unlatching is stirred and rises to reaction temperature and starts instead
Should.When hydrogenation reaction proceeds to 3h, the conversion ratio of o-chloronitrobenzene has reached 98.5%, and the selectivity of o-chloraniline is
99.4%.
Embodiment 3
By 4.04gFe (NO3)3·9H2O、11.632gNi(NO3)2·6H2O is dissolved in 100mL deionized waters, ultrasound
5min, is sufficiently mixed, and is designated as solution first.
By the 2.56g NaOH and H of 125 μ L mass fractions 30%2O2It is dissolved in 100mL deionized waters, ultrasonic 5min, fully
Mixing, is designated as solution second.
Two kinds of solution are slowly mixed together and are added in colloid mill at room temperature, rotating speed is controlled for 3000rpm, with 2min
It is transferred in polytetrafluoroethylliner liner after being stirred vigorously, closed rear room temperature static crystallization 24h.After reaction terminates, centrifuge washing is extremely
Neutrality, freeze-drying obtains the LDH precursors of nanocatalyst.
0.5gNiFe-LDH is taken to be fully ground to it in mortar and mixed with 0.19g dicyandiamides and 1.31g melamines
It is even, it is placed in porcelain boat, 5 DEG C of min-1 are warming up to 500 DEG C and are incubated 6h in nitrogen atmosphere, and core shell structure is urged after grinding
Agent.Wherein dilval nano-particle average grain diameter is 12nm, and the weight/mass percentage composition of nickel element is 35.8% in catalyst,
The weight/mass percentage composition of Fe is 9.8%, and the specific surface area of catalyst is 110m2/g。
In o-chloronitrobenzene selective hydrogenation, first to addition 0.1g catalyst, 50ml ethanol, 0.5g in reactor
O-chloronitrobenzene.Then, tighten reactor, ventilation 10 times filled with hydrogen, it is ensured that be full of hydrogen in system, and build the pressure one hour with
Ensure the seal of reactor.Hydrogen to system pressure 0.5MPa is finally passed through, unlatching is stirred and rises to reaction temperature and starts instead
Should.When hydrogenation reaction proceeds to 3h, the conversion ratio of o-chloronitrobenzene has reached 97.4%, and the selectivity of o-chloraniline is
98.1%.
Embodiment 4
By 4.04gFe (NO3)3·9H2O、8.724gNi(NO3)2·6H2O is dissolved in 100mL deionized waters, ultrasonic 5min,
It is sufficiently mixed, is designated as solution first.
By the 2.56g NaOH and H of 125 μ L mass fractions 30%2O2It is dissolved in 100mL deionized waters, ultrasonic 5min, fully
Mixing, is designated as solution second.
Two kinds of solution are slowly mixed together and are added in colloid mill at room temperature, rotating speed is controlled for 3000rpm, with 2min
It is transferred in polytetrafluoroethylliner liner after being stirred vigorously, closed rear room temperature static crystallization 24h.After reaction terminates, centrifuge washing is extremely
Neutrality, freeze-drying obtains the LDH precursors of nanocatalyst.
0.5gNiFe-LDH and 0.127g dicyandiamides and 0.873g melamines are taken, is placed in porcelain boat, in blanket of nitrogen
5 DEG C of min in enclosing-1It is warming up to 500 DEG C and is incubated 6h, catalyst with core-casing structure after grinding.Wherein dilval nano-particle is put down
Equal particle diameter is 17nm, and the weight/mass percentage composition of nickel element is that the weight/mass percentage composition of 30.6%, Fe is 11.3% in catalyst, is urged
The specific surface area of agent is 130m2/g。
In o-chloronitrobenzene selective hydrogenation, first to addition 0.1g catalyst, 50ml ethanol, 0.5g in reactor
O-chloronitrobenzene.Then, tighten reactor, ventilation 10 times filled with hydrogen, it is ensured that be full of hydrogen in system, and build the pressure one hour with
Ensure the seal of reactor.Hydrogen to system pressure 0.5MPa is finally passed through, unlatching is stirred and rises to reaction temperature and starts instead
Should.When hydrogenation reaction proceeds to 3h, the conversion ratio of o-chloronitrobenzene has reached 96.9%, and the selectivity of o-chloraniline is
97.5%.
It is understood that the embodiment of above principle being intended to be merely illustrative of the present and the exemplary implementation for using
Mode, but the invention is not limited in this.For those skilled in the art, essence of the invention is not being departed from
In the case of god and essence, various changes and modifications can be made therein, and these variations and modifications are also considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of nitrogen-doped carbon coated core-shell structure dilval nanocatalyst, it is characterised in that
1) by nickel nitrate and ferrous sulfate mixed aqueous solution, NaOH and H2O2Mixed aqueous solution is placed in colloid mill fully in equal volume
After stirring 1-5min, it is transferred in polytetrafluoroethylliner liner, closed rear room temperature static crystallization 12-36h, after reaction terminates, centrifugation
To neutrality, freeze-drying obtains NiFe-LDH precursors for washing；
2) prepared NiFe-LDH precursors are mixed with melamine and dicyandiamide mixture, is placed in nitrogen atmosphere stove
In, 2-10h is incubated at being warming up to 500~650 DEG C, obtain nitrogen-doped carbon coated core-shell structure dilval nanocatalyst.
2. the preparation method of nitrogen-doped carbon coated core-shell structure dilval nanocatalyst according to claim 1, its
It is characterised by, step 1) in, the Ni of nickel nitrate and ferrous sulfate mixed aqueous solution2+Concentration be 0.03~0.1mol/L.
3. the preparation method of nitrogen-doped carbon coated core-shell structure dilval nanocatalyst according to claim 1, its
It is characterised by, step 1) in, the Fe of nickel nitrate and ferrous sulfate mixed aqueous solution2+Concentration be 0.01~0.04mol/L.
4. the preparation method of nitrogen-doped carbon coated core-shell structure dilval nanocatalyst according to claim 1, its
It is characterised by, step 1) in, NaOH and H2O2The concentration of NaOH is 0.06~0.23mol/L in mixed aqueous solution.
5. the preparation method of nitrogen-doped carbon coated core-shell structure dilval nanocatalyst according to claim 1, its
It is characterised by, step 1) in, NaOH and H2O2In mixed aqueous solution, H2O2Consumption be the ratio between with ferrous sulfate molar concentration
It is 1~2.5：1.
6. the preparation method of nitrogen-doped carbon coated core-shell structure dilval nanocatalyst according to claim 1, its
It is characterised by, step 2) in, nanocatalyst precursor is 0.5 with the mass ratio of melamine and dicyandiamide mixture：2~1, three
The mol ratio of poly cyanamid and dicyandiamide is 0.3：0.7~1.
7. the nitrogen-doped carbon coated core-shell structure dilval nanocatalyst that method according to claim 1 is prepared
The application of catalysis o-chloronitrobenzene hydrogenation reaction.
8. application according to claim 7, it is characterised in that the condition of described catalysis o-chloronitrobenzene hydrogenation reaction
For：The nitrogen-doped carbon coated core-shell structure dilval nanocatalyst and the second of o-chloronitrobenzene that will be prepared in claim 1
Alcoholic solution is added in autoclave, leads to the H of 0.5MPa2, temperature rises to 80 DEG C of reactions.
9. application according to claim 8, it is characterised in that after reaction 3h, the conversion ratio of o-chloronitrobenzene and to adjacent chlorine
Aniline is selectively respectively 95~100% and 98~100%.
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| CN117123281A (en) * | 2023-08-03 | 2023-11-28 | 宁夏大学 | Long-acting catalyst of carbon-coated Fe-Ni alloy, and preparation method and application thereof |
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